EP2508864B1 - Verfahren zur Rückgewinnung von Metall - Google Patents

Verfahren zur Rückgewinnung von Metall Download PDF

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Publication number
EP2508864B1
EP2508864B1 EP12163024.8A EP12163024A EP2508864B1 EP 2508864 B1 EP2508864 B1 EP 2508864B1 EP 12163024 A EP12163024 A EP 12163024A EP 2508864 B1 EP2508864 B1 EP 2508864B1
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EP
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Prior art keywords
chelating agent
complex
group
metal
aqueous solution
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EP12163024.8A
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English (en)
French (fr)
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EP2508864A3 (de
EP2508864A2 (de
Inventor
Yuka Shimomura
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Arkray Inc
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Arkray Inc
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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/40—Concentrating samples
    • G01N1/4044—Concentrating samples by chemical techniques; Digestion; Chemical decomposition
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/20—Metals
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/40—Concentrating samples
    • G01N1/4055—Concentrating samples by solubility techniques
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
    • G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
    • G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
    • G01N33/84—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing involving inorganic compounds or pH
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/40—Concentrating samples
    • G01N1/4055—Concentrating samples by solubility techniques
    • G01N2001/4061—Solvent extraction
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the present invention relates to a method for recovering a metal.
  • metals such as mercury, cadmium, lead, and arsenic are accumulated in human bodies, which results in adverse effects on health. Therefore, it is important to analyze metals in biological samples such as urine and the like and samples of food and beverage such as water and the like.
  • a pretreatment In analysis of a metal, generally, as a pretreatment, foreign substances are removed from a sample, and a metal is separated from the resultant sample, and the separated metal is analyzed.
  • a solvent extraction is widely used.
  • the solvent extraction is a method in which a metal in a sample is extracted in an organic medium by utilizing the polarity of a chelating agent to be bound to the metal according to the difference in distribution coefficient of the metal to an aqueous medium and the organic medium.
  • the metal can be further concentrated by evaporating the organic medium after the extraction.
  • a dithizone method using, as the chelating agent, 1,5-diphenyl-3-thiocarbazone (hereinafter, also referred to as "dithizone”) that is insoluble in an aqueous medium under the acidic condition is defined in JIS, for example (see, Mercury Analysis Manual, Ministry of the Environment, March 2004, Japanese Patent No. 2969226 ).
  • dithizone method first, dithizone and a liquid sample such as urine are mixed under the acidic condition, and thus a complex between the dithizone and a metal being in the liquid sample is formed in the mixture. Subsequently, an organic medium such as carbon tetrachloride or chloroform is added to the mixture.
  • the complex is extracted in the organic medium because the distribution coefficient of the complex to the aqueous medium is different from that of the complex to the organic medium. Thereafter, this organic medium is recovered.
  • the metal is recovered as the complex from the liquid sample.
  • the organic medium is evaporated, the metal can be further concentrated.
  • the present invention is intended to provide a method for recovering a metal, capable of recovering a metal easily without requiring the use of an organic medium.
  • the present invention provides a method for recovering a metal as defined in claim 1.
  • kits for recovery of a metal for use in the method for recovering a metal of the present invention, the kit including: a first chelating agent; and a second chelating agent.
  • an analysis apparatus including: a pH adjusting unit for adjusting a pH; a first mixing unit for mixing a first chelating agent and a sample; a complex recovering unit for recovering a first complex between the first chelating agent and a metal being in the sample from a first mixture containing the first chelating agent and the sample; a second mixing unit for mixing an aqueous solution of a second chelating agent and the first complex; a liquid fraction recovering unit for recovering a liquid fraction containing a second complex between the metal derived from the first complex and the second chelating agent, dissolved therein, from a second mixture of the aqueous solution of the second chelating agent and the first complex; a metal recovering unit for recovering the metal being in the second complex, and an analyzing unit for analyzing the recovered metal, wherein the analysis apparatus is for use in a method for analyzing a metal.
  • a metal can be recovered easily by utilizing the difference in solubility between the first chelating agent and the second chelating agent in an aqueous medium without substantially using an organic medium. Therefore, the present invention is really useful in clinical examinations of samples derived from biological bodies and environmental testing, for example.
  • a method for recovering a metal (hereinafter merely referred to as the "metal recovering method") of the present invention is defined in claim 1.
  • the chelating agent preferably is a chelating agent comprising a sulfur-containing group.
  • the sulfur-containing group is a functional group having a sulfur atom.
  • the sulfur-containing group may be a thioketone group or comprises a thioketone group, for example.
  • the thioketone group is not particularly limited and examples thereof include a thiocarbazone group, a thiosemicarbazone group, a thiocarbadiazone group, a thiourea group, a thiosemicarbazide group, and a rubeamate group.
  • Thiocarbazone group Thiosemicarbazone group Thiocarbadiazone group Thiourea group Thiosemicarbazide group Rubeamate group
  • the first chelating agent can be, for example, a chelating agent represented by the structural formula (1) or (2).
  • R 1 and R 2 each represents a phenyl group. That is, the first chelating agent represented by the structural formula (1) is a chelating agent comprising a thiocarbazone group and can be 1,5-diphenyl-3-thiocarbazone. Hereinafter, the first chelating agent is also referred to as dithizone.
  • the chelating agent represented by the structural formula (1) may be, for example, a salt.
  • R 3 represents hydrogen, an alkyl group, or a phenyl group.
  • the chelating agent represented by the structural formula (2) may be, for example, a salt.
  • the alkyl group is not particularly limited, and examples thereof include straight-chain or branched alkyl groups.
  • the carbon number of the alkyl group is, for example, from 1 to 6.
  • Examples of the straight-chain or branched alkyl groups include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, an isopentyl group, a neopentyl group, a n-hexyl group, an isohexyl group, a n-heptyl group, a n-octyl group, a n-nonyl group, and a n-decyl group. Any hydrogen in the alkyl group may be substituted, for example.
  • Any hydrogen in the phenyl group may be substituted, for example.
  • the hydrogen in the phenyl group may be substituted by halogen or an alkali metal such as sodium or potassium when substituted.
  • the chelating agent represented by the structural formula (2) is, for example, a chelating agent comprising a thiosemicarbazone group, and examples thereof include glyoxaldithiosemicarbazone and (1E,2E)-aminocarbothioyl hydrazono phenylethanal thiosemicarbazone.
  • the chelating agent preferably is a chelating agent comprising a sulfur-containing group as mentioned above.
  • the sulfur-containing group can be, for example, a thioketone group.
  • the chelating agent comprising a thioketone group can be, for example, a chelating agent comprising at least one selected from the group consisting of a thiocarbazone group, a thiosemicarbazone group, a thiocarbadiazone group, a thiourea group, a thiosemicarbazide group, and a rubeamate group.
  • the following chelating agents are illustrated. In the present invention, the following chelating agents are mere examples, and the present invention is not limited thereby.
  • the second chelating agent is, for example, preferably a chelating agent comprising a thiol group.
  • the second chelating agent is not particularly limited and can be, for example, a chelating agent comprising a structure represented by the structural formula (3), (4), or (5).
  • the second chelating agent comprising a structure represented by the structural formula (3) is meso-2,3-dimercapto succinic acid.
  • the second chelating agent is also referred to as DMSA.
  • R 4 represents an alkyl group with the carbon number of 1 or 2 or is not present
  • Y represents The alkyl group with the carbon number of 1 or 2 is, for example, a methyl group or an ethyl group.
  • Examples of the second chelating agent comprising a structure represented by the structural formula (4) include thiopronine (N-(2-mercaptopropionyl)glycine) represented by the following structural formula (4-1), DMPS (2,3-dimercapto-1-propanesulfonic acid sodium salt) represented by the following structural formula (4-2), and cysteine (2-amino-3-sulfanyl propanoic acid) represented by the following structural formula (4-3).
  • R 5 represents an aromatic hydrocarbon group
  • Y represents
  • R 5 represents an aromatic hydrocarbon group with the carbon number from 1 to 10, for example, and examples thereof include a phenyl group, a benzyl group, a tolyl group, and a naphthyl group.
  • the second chelating agent comprising a structure represented by the structural formula (5) can be, for example, a chelating agent represented by the following structural formula (5-1).
  • R 6 represents a hydroxyl group, for example.
  • the chelating agent represented by the structural formula (5-1) may be a salt, for example, and examples of the salt include alkali metal salts such as a sodium salt and a potassium salt.
  • Specific examples of the chelating agent represented by the structural formula (5-1) include thiosalicylic acid represented by the following structural formula (5-2) and sodium thiosalicylate represented by the following structural formula (5-3).
  • Each of the first chelating agent and the second chelating agent may be, for example, any of tautomers and streoisomers of the above-mentioned compounds.
  • Examples of the isomers include geometric isomers, conformers, and stereoisomers.
  • Each of the first chelating agent and the second chelating agent may be, for example, any of hydrates of the above-mentioned compounds.
  • Each of the first chelating agent and the second chelating agent may be, for example, any of salts of the above-mentioned compounds, and examples of the salts include alkali metal salts such as a sodium salt and a potassium salt.
  • any hydrogen may be substituted, for example, and specifically, any hydrogen may be substituted by an alkali metal such as halogen, sodium, or potassium, for example.
  • an alkali metal such as halogen, sodium, or potassium
  • the first chelating agent and the second chelating agent commercially available products may be used.
  • the thiopronine is available from KANTO CHEMICAL CO., INC., Tokyo Chemical Industry Co., Ltd., Wako Pure Chemical Industries, Ltd., or the like, for example.
  • the DMPS is available from Wako Pure Chemical Industries, Ltd. or the like, for example.
  • the cysteine is available from NACALAI TESQUE, INC. or the like, for example.
  • the first chelating agent may be used alone or in a combination of two or more of them, for example.
  • the second chelating agent may be used alone or in a combination of two or more of them.
  • the combination of the first chelating agent and the second chelating agent is not particularly limited. Examples of the combination include: combinations of the first chelating agent represented by the structural formula (1) with the second chelating agent comprising a structure represented by the structural formula (3), the second chelating agent comprising a structure represented by the structural formula (4), and the second chelating agent comprising a structure represented by the structural formula (5); and combinations of the first chelating agent represented by the structural formula (2) with the second chelating agent comprising a structure represented by the structural formula (3), the second chelating agent comprising a structure represented by the structural formula (4), and the second chelating agent comprising a structure represented by the structural formula (5).
  • any of the combinations of the first chelating agent represented by the structural formula (1) with the second chelating agent comprising a structure represented by the structural formula (3), the second chelating agent comprising a structure represented by the structural formula (4), and the second chelating agent comprising a structure represented by the structural formula (5) and the combination of the first chelating agent represented by the structural formula (2) and the second chelating agent comprising a structure represented by the structural formula (4) is preferable.
  • the combination include a combination of dithizone and DMSA, a combination of dithizone and thiopronine or DMPS, a combination of dithizone and sodium thiosalicylate, and a combination of glyoxaldithiosemicarbazone and thiopronine.
  • the metal to be recovered is not particularly limited. Examples thereof include Bi (bismuth), Hg (mercury), Cd (cadmium), Pd (palladium), Zn (zinc), Tl (thallium), Ag (silver), Pb (lead), and As (arsenic).
  • the form of the metal in the sample is not particularly limited and may be, for example, a single metal, an alloy of metals, or a metal-containing compound.
  • the metal-containing compound may be, for example, a metal-containing organic compound or a metal-containing inorganic compound. In the case where the metal is Hg, Hg may be, for example, organic mercury or inorganic mercury.
  • the metal to be recovered may be, for example, one kind or two or more kinds. In the metal recovering method of the present invention, two or more kinds of metals can be recovered at the same time by a single recovering treatment, for example.
  • the sample is not particularly limited.
  • examples thereof include a sample derived from a biological body, a sample derived from the environment, a chemical substance, and a pharmaceutical.
  • the chemical substance include reagents, pesticides, and cosmetics.
  • the sample derived from a biological body is not particularly limited, and examples thereof include urine, blood, hair, and umbilical cords.
  • examples of the blood sample include erythrocytes, whole blood, sera, and plasma. Among them, the urine sample is preferable.
  • the sample derived from the environment is not particularly limited, and examples thereof include an organism, food, water, the ground, and atmosphere and air. Examples of the organism include animals such as the human and fish and shellfish and plants.
  • Examples of the food sample include a fresh food and a processed food.
  • Examples of the water sample include drinking water, groundwater, river water, seawater, and domestic sewage.
  • a fluid sample is preferable as the sample because it can be handled easily, for example.
  • An undiluted liquid or a diluted liquid obtained by suspending, dispersing, or dissolving the sample in a medium may be used as the liquid sample, for example.
  • a diluted liquid obtained by suspending, dispersing, or dissolving the solid in a medium may be used as the liquid sample, for example.
  • the medium is referred to as a dilution medium.
  • the dilution medium is not particularly limited, and examples thereof include water and a buffer solution.
  • the buffer solution is not particularly limited and examples thereof include a tris(hydroxymethyl)aminomethane buffer solution (tris buffer solution), a phosphate buffer solution, an acetate buffer solution, a borate buffer solution, a citrate buffer solution, a veronal buffer solution, and various Good buffer solutions.
  • concentration of the buffer solution is not particularly limited and is, for example, from 10 to 100 mmol/L.
  • the first chelating agent maintains the state of being undissolved in the first mixture under the first pH condition. Therefore, when a metal is present in the sample, a first complex between the first chelating agent and the metal being in the sample is formed in the first mixture.
  • the first chelating agent is, for example, preferably in the state of not being dissolved in the first mixture
  • the first pH condition can be set as appropriate according to the kinds of the first chelating agent to be used and the metal to be recovered.
  • the pH condition for insolubilization is not particularly limited.
  • the first pH condition can be, for example, the acidic condition (pH 5 or less), the neutral condition (pH 6 to 7), and the alkaline condition (more than pH 7 to pH 8 or less).
  • the upper limit thereof is, for example, pH 8, and the lower limit thereof is, for example, pH 1. Specific examples thereof include pH 1 to 8, pH 2 to 8, and pH 1 to 2.
  • the form of the first chelating agent at the time of mixing with the sample is not particularly limited, and the first chelating agent may be in the dry state (or also referred to as the solid state) or in the liquid state, for example.
  • the first chelating agent is preferably a first chelating agent-dispersion liquid obtained by dispersing the first chelating agent in a non-organic medium in which the first chelating agent cannot be dissolved.
  • the non-organic medium in which the first chelating agent is dispersed is referred to as a "dispersion medium".
  • the dispersion medium is, for example, a non-organic medium (aqueous medium) under the first pH condition.
  • the aqueous medium is not particularly limited, and for example, water, an aqueous solution, a buffer solution, or the like can be used.
  • the aqueous medium and the second chelating agent are mixed, and thereafter, the condition of the mixture thus obtained is adjusted to the second pH condition.
  • a method for adjusting the condition of the mixture is not particularly limited, and in the method, the acidic reagent, the alkaline reagent, and the neutral reagent can be used as appropriate, for example.
  • the concentration of the second chelating agent in the second chelating agent aqueous solution is not particularly limited and is, for example, from 5 to 300 mg/mL.
  • the treatment conditions for forming a second complex are not particularly limited, and the treatment temperature is, for example, room temperature, and the treatment time is, for example, from 10 seconds to 120 minutes. Specifically, the treatment temperature is, for example, preferably in the range from 10 seconds to 10 minutes, particularly preferably from 10 seconds to 5 minutes.
  • the concentration of the second chelating agent in the second chelating agent aqueous solution is, for example, from 5 to 20 mg/mL, and the pH of the second chelating agent aqueous solution is, for example, from 2 to 6, preferably from 4 to 6.
  • the pH of the second mixture of the first complex and the second chelating agent aqueous solution is, for example, from 2 to 6, preferably from 4 to 6.
  • the concentration of the second chelating agent in the second chelating agent aqueous solution is, for example, from 15 to 300 mg/mL, and the pH of the second chelating agent aqueous solution is, for example, from 1 to 6, preferably from 1 to 3, more preferably 1.
  • the pH of the second mixture of the first complex and the second chelating agent aqueous solution is, for example, from 1 to 6, preferably from 1 to 3, and more preferably 1.
  • the kit for recovery of a metal not being part of the present invention is a kit for recovery of a metal, for use in the metal recovering method of the present invention, the kit including: a first chelating agent; and a second chelating agent.
  • the first chelating agent and the second chelating agent can be explained with reference to the explanation of the metal recovering method of the present invention, for example. It is preferred that the first chelating agent and the second chelating agent are stored in different containers.
  • the analysis apparatus not being part of the present invention is, as mentioned above, an analysis apparatus including: a pH adjusting unit for adjusting a pH; a first mixing unit for mixing a first chelating agent and a sample; a complex recovering unit for recovering a first complex between the first chelating agent and a metal being in the sample from a first mixture containing the first chelating agent and the sample; a second mixing unit for mixing an aqueous solution of a second chelating agent and the first complex; a liquid fraction recovering unit for recovering a liquid fraction containing a second complex between the metal derived from the first complex and the second chelating agent, dissolved therein, from a second mixture of the aqueous solution of the second chelating agent and the first complex; a metal recovering unit for recovering the metal being in the second complex, and an analyzing unit for analyzing the recovered metal, wherein the analysis apparatus is for use in a method for analyzing a metal.
  • the analysis apparatus is for use in the method for analyzing a metal explained above.
  • the pH adjusting unit includes an acid adding unit and an alkali adding unit, for example.
  • the mixing unit for mixing the first chelating agent and the sample is referred to as a first mixing unit, for example, the mixing unit for mixing a second chelating agent aqueous solution and the first complex is referred to as a second mixing unit, for example.
  • the second adding unit includes: a suction-and-discharge unit for sucking and discharging the second chelating agent aqueous solution arranged inside or outside the analysis apparatus; and a controlling unit for controlling the amount of the second chelating agent aqueous solution to be sucked and/or discharged, for example.
  • the suction-and-discharge unit and the controlling unit can be, for example, the same as mentioned above.
  • liquid fraction recovering unit examples include a centrifuge, a filtration unit, and a freeze-dryer.
  • the metal recovering unit is, for example, a unit for decomposing the second chelating agent in the second complex.
  • the unit include ashers such as a wet asher and a dry asher.
  • the analysis apparatus preferably further include a pH measuring unit.
  • the pH measuring unit can be, for example, a pH meter.
  • the analysis apparatus preferably includes an introducing unit for introducing a sample, for example.
  • the introducing unit is, for example, preferably a suction-and-discharge unit for sucking and discharging a sample.
  • the above-mentioned metal analyzing method can be performed with the analysis apparatus described above.
  • the usage of the analysis apparatus is illustrated below.
  • the sample, the first chelating agent, the second chelating agent aqueous solution, and an acidic reagent as a pH adjusting reagent are arranged inside or outside the analysis apparatus.
  • the analysis apparatus may further include an output unit for outputting an analysis result with respect to the metal, for example.
  • an output unit for outputting an analysis result with respect to the metal, for example.
  • a monitor or a printer can be used, for example.
  • Dithizone (produced by Fluka) as a first chelating agent was dissolved in t-butyl alcohol (produced by NACALAI TESQUE, INC.). This solution thus obtained was dispensed in 15 mL-capacity conical tubes made of PP (produced by Nunc) so that the amount of the dithizone in each of the tubes became 1.5 mg. The tubes each containing the solution was then subjected to freeze-drying.
  • Urine samples each with the mercury concentration of 10 pg/L were prepared in the same manner as in Example A1. 5N hydrochloric acid (produced by NACALAI TESQUE, INC.) or 5N sodium hydroxide (produced by NACALAI TESQUE, INC.) was added to 5 mL each of the urine samples so that the pH's of the respective urine samples were adjusted to 2, 3, 4, 6.8, and 8. Furthermore, as negative controls, five types of distilled waters with the respective pH's of 2, 3, 4, 6.8, and 8 were used.
  • a second chelating agent aqueous solution was prepared using DMSA and a 3Na phosphate aqueous solution in the same manner as in Example A1.
  • Mercury-concentrated samples were prepared in the same manner as in Example A1. Then, the mercury-concentrated samples were subjected to ashing, and thereafter mercury in each of the mercury-concentrated samples thus obtained was qualitatively determined using an atomic absorption spectrometer.
  • a urine sample was prepared in the same manner as in Example A1 except that the mercury concentration was set to 80 ⁇ g/L, and the pH of the urine sample was adjusted to 1 to 2.
  • Tubes each containing dithizone (produced by Fluka) as a first chelating agent were subjected to freeze-drying in the same manner as in Example A1.
  • Thiopronine (produced by KANTO CHEMICAL CO., INC.) as a second chelating agent was dissolved in 0.1 mol/L nitric acid aqueous solution so as to have the thiropronine concentrations from 100 to 1000 mmol/L.
  • second chelating agent aqueous solutions were prepared.
  • the pH's of the second chelating aqueous solutions were 1.
  • Mercury-concentrated samples were prepared in the same manner as in Example A1 except that the above-mentioned freeze-dried first chelating agent and the above-mentioned second chelating agent aqueous solutions were used. Then, the mercury-concentrated samples were treated in the same manner as in Example A1, and the mercury concentration of each of the mercury-concentrated samples thus obtained was determined. Furthermore, the mercury concentration of the urine sample was determined in the same manner as in Example A1 using an atomic absorption spectrometer. Then, the recovery rate and concentration rate of mercury were determined in the same manner as in Example A1.
  • a second chelating agent aqueous solution was prepared using DMPS (produced by Tokyo Chemical Industry Co., Ltd.) as a second chelating agent as substitute for thiopronine.
  • the pH of the second chelating agent aqueous solution was 1.
  • Mercury was recovered from an urine sample in the same manner as in Example B1 for using the above-described second chelating agent aqueous solution. The results are shown in Table 4 below. As shown in Table 4, mercury could be recovered from the urine sample and concentrated to about 18- to 37-fold. From these results, it was found that according to the present invention, mercury could be recovered and concentrated from the urine sample without requiring the use of an organic medium.
  • DMPS concentration 100 200 500 750 1000 Mercury concentration before concentration 84.87 84.87 84.87 84.87 84.87 ( ⁇ g/L) after concentration 1496.80 2125.91 2685.18 3113.06 3016.25 Recovery rate (%) 35.27 50.10 63.27 73.36 71.08 Concentration rate (-fold) 17.64 25.05 31.64 36.68 35.54
  • An urine sample was prepared in the same manner as in Example A1, and the pH of the urine sample was adjusted to about 1 to 2.
  • Tubes each containing dithizone (produced by Fluka) as a first chelating agent were subjected to freeze-drying in the same manner as in Example A1.
  • Sodium thiosalicylate (produced by Tokyo Chemical Industry Co., Ltd.) as a second chelating agent was dissolved in a 0.1 mol/L nitric acid aqueous solution so as to have the sodium thiosalicylate concentration of 500 mmol/L. Thereafter, the sodium thiosalicylate was dissolved using 5N NaOH. Thus, a second chelating agent aqueous solution was prepared. The pH of the second chelating agent aqueous solution was 4.
  • Mercury-concentrated samples were prepared in the same manner as in Example A1 except that the above-mentioned freeze-dried first chelating agent and the above-mentioned second chelating agent aqueous solution were used. Then, the mercury-concentrated samples were treated in the same manner as in Example A1, and the mercury concentration of each of the mercury-concentrated samples thus obtained was determined. Then, the mercury-concentrated samples were treated in the same manner as in Example A1, and the mercury concentration of each of the mercury-concentrated samples thus obtained was determined. Furthermore, the mercury concentration of the urine sample was determined in the same manner as in Example A1 using an atomic absorption spectrometer. Then, the recovery rate and concentration rate of mercury were determined in the same manner as in Example A1.
  • An urine sample (pH 6 to 7) was prepared, and the pH of the urine sample was adjusted to 1 to 2, in the same manner as in Example A1.
  • the predetermined amounts (1.5, 34.5, and 7.5mg) of glyoxaldithiosemicarbazone (produced by Wako Pure Chemical Industries, Ltd.) as a first chelating agent were weighted into the respective 15 mL-capacity conical tubes made of polypropylene (PP) (produced by Nunc).
  • PP polypropylene
  • Thiopronine (produced by KANTO CHEMICAL CO., INC.) was dissolved in a 0.1 mol/L nitric acid aqueous solution so as to have the thiopronine concentration of 500 mmol/L.
  • a second chelating agent aqueous solution was prepared.
  • the pH of the second chelating agent aqueous solution was 1.
  • the whole amount of the urine sample was added to each of the tubes each containing the first chelating agent, which was then shaken for 5 minutes at room temperature so as to mix the urine sample and the first chelating agent.
  • a complex (first complex) between the first chelating agent and mercury was formed.
  • mercury-concentrated samples were prepared in the same manner as in Example A1 except that the above-mentioned second chelating agent aqueous solution was used.
  • Example A1 the mercury-concentrated samples were treated in the same manner as in Example A1, and the mercury concentration of each of the mercury-concentrated samples thus obtained was determined. Furthermore, the mercury concentration of the urine sample was determined in the same manner as in Example A1 using an atomic absorption spectrometer. Then, the recovery rate and concentration of mercury were determined in the same manner as in Example A1.
  • glyoxaldithiosemicarbazone produced by Wako Pure Chemical Industries, Ltd.
  • DMSA, DMPS, L-cysteine, and sodium thiosalicylate were used as second chelating agents.
  • Mercury was recovered from an urine sample in the same manner as in Example D1 except that these chelating agents were used.
  • DMSA was mixed with a 0.1 mol/L nitric acid aqueous solution, and then, 5N NaOH was added thereto so as to dissolve the DMSA.
  • a 0.1 mol/L nitric acid aqueous solution was added to his aqueous solution thus obtained so as to have the DMSA concentration of 500 mmol/L.
  • a DMSA aqueous solution was prepared.
  • the pH of the DMSA aqueous solution was 4.
  • DMPS was dissolved in a 0.1mol/L nitric acid aqueous solution so as to have the DMPS concentration of 500 mmol/L.
  • a DMPS aqueous solution was prepared.
  • the pH of the DMPS aqueous solution was 4.
  • L-cysteine was dissolved in 0.1 mol/L nitric acid aqueous solution so as to have the L-cysteine concentration of 500 mmol/L.
  • an L-cysteine aqueous solution was prepared.
  • the pH of the L-cysteine aqueous solution was 1.
  • Na thiosalicylate was mixed with a 0.1 mol/L nitric acid aqueous solution, and further 5N NaOH was added thereto, so as to dissolve the Na thiosalicylate.
  • a 0.1 mol/L nitric acid aqueous solution was added to this aqueous solution thus obtained so as to have the Na thiosalicylate concentration of 500 mmol/L.
  • a Na thiosalicylate aqueous solution was prepared.
  • the pH of the Na thiosalicylate aqueous solution was 4.
  • a 0.34 mol/L sodium chloride aqueous solution containing 0.01% poly(oxyethylene)sorbitan monolaurate (Tween-20) was prepared.
  • a lead standard solution (produced by Wako Pure Chemical Industries, Ltd.) was added to the aqueous solution thus obtained so as to have the lead concentration of 0.5 mg/L.
  • a liquid sample was prepared.
  • a control sample (with the leas concentration of 0 mg/L) was prepared by adding a 0.1 mol/L nitric acid aqueous solution as substitute for the lead standard solution.
  • the pH's of the liquid sample and the control sample were 6.
  • Dithizone (produced by Fluka) was dissolved in t-butyl alcohol (produced by NACALAI TESQUE, INC.). This solution thus obtained was dispensed in 1 mL-capacity tubes made of PP (produced by produced by Nichiryo Co., Ltd.) so that the amount of the dithizone in each of the tubes became 1.5 mg. The tubes each containing the solution were then subjected to freeze-drying.
  • the lead-concentrated sample was subjected to wet ashing. Thus, the dithizone in the complex was decomposed. Then, the lead concentration of the lead-concentrated sample thus obtained was determined by mass spectrometry using an ICP mass spectrometer (ICP-MS, trade name: ICPM-8500, produced by Shimadzu Corporation). Furthermore, the lead concentration of the control sample was determined in the same manner as described above.
  • ICP-MS ICP mass spectrometer
  • a metal can be recovered easily by utilizing the difference in solubility between the first chelating agent and the second chelating agent in an aqueous medium without using an organic medium. Therefore, the present invention is really useful in critical examinations of samples derived from biological bodies and environmental testing, for example.

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Claims (13)

  1. Verfahren zum Rückgewinnen eines Metalls aus einer flüssigen Probe, wobei das Verfahren die Schritte umfasst:
    Herstellen einer ersten Mischung aus einem ersten Chelatbildner und der flüssigen Probe, wobei, um einen ersten Komplex zwischen dem ersten Chelatbildner und dem Metall zu bilden, die erste Mischung einen pH-Wert-Zustand aufweist, bei dem der erste Komplex nicht aufgelöst ist;
    Rückgewinnen des ersten nicht aufgelösten Komplexes aus der ersten Mischung;
    Herstellen einer zweiten Mischung aus dem nicht aufgelösten ersten Komplex und einer wässrigen Lösung eines zweiten Chelatbildners, wobei, um das Metall aus dem ersten Komplex zu dissoziieren und einen zweiten Komplex zwischen dem aus dem ersten Komplex abgeleiteten Metall und dem zweiten Chelatbildner zu bilden, die wässrige Lösung des zweiten Chelatbildners einen pH-Wert-Zustand aufweist, bei dem der erste Chelatbildner darin unlöslich ist, und die zweite Mischung einen pH-Wert-Zustand aufweist, bei dem der erste Chelatbildner und der erste Komplex nicht aufgelöst sind und bei dem der zweite Komplex aufgelöst ist; und
    Rückgewinnen des Metalls durch Rückgewinnen einer flüssigen Fraktion aus der zweiten Mischung, die den zweiten Komplex darin aufgelöst enthält.
  2. Verfahren nach Anspruch 1, wobei
    der erste Chelatbildner eine schwefelenthaltende Gruppe umfasst.
  3. Verfahren nach Anspruch 2, wobei
    die schwefelenthaltende Gruppe eine Thioketongruppe umfasst.
  4. Verfahren nach Anspruch 1, wobei
    der erste Chelatbildner mindestens eines umfasst, ausgewählt aus der Gruppe, bestehend aus einer Thiocarbazongruppe, einer Thiosemicarbazongruppe, einer Thiocarbadiazongruppe, einer Thioharnstoffgruppe, einer Thiosemicarbazidgruppe und einer Rubeamatgruppe.
  5. Verfahren nach Anspruch 1, wobei
    der erste Chelatbildner mindestens einer von 1,5-Diphenyl-3-thiocarbazon, Glyoxaldithiosemicarbazon und (1E,2E)-Aminocarbothioylhydrazonophenylethanalthiosemicarbazon ist.
  6. Verfahren nach einem der vorstehenden Ansprüche, wobei
    der zweite Chelatbildner eine Thiolgruppe umfasst.
  7. Verfahren nach einem der Ansprüche 1 bis 5, wobei
    der zweite Chelatbildner eine Verbindung von Strukturformel (3) ist:
    Figure imgb0028
     oder eine Verbindung, umfassend eine Struktur, dargestellt durch mindestens eine ausgewählt aus der Gruppe, bestehend aus Strukturformeln (4) und (5):
    Figure imgb0029
    Figure imgb0030
     wobei
    R4 eine Alkylgruppe oder eine Aminoalkylgruppe darstellt, jeweils mit einer Kohlenstoffanzahl von 1 oder 2, oder abwesend ist,
    R5 eine aromatische Kohlenwasserstoffgruppe darstellt, und
    Y darstellt
    Figure imgb0031
  8. Verfahren nach einem der Ansprüche 1 bis 5, wobei
    der zweite Chelatbildner mindestens einer ausgewählt aus der Gruppe ist, bestehend aus meso-2,3-Dimercaptobernsteinsäure, N-(2-Mercaptopropionyl)glycin, 1,2-Dimercapto-1-natriumpropansulfonat, Cystein, Thiosalicylsäure und Natriumthiosalicylat.
  9. Verfahren nach einem der vorstehenden Ansprüche, wobei
    die erste Mischung einen pH-Wert-Zustand aufweist, der pH-Wert 8 oder weniger ist.
  10. Verfahren nach einem der vorstehenden Ansprüche, wobei die erste Mischung einen pH-Wert-Zustand aufweist, der pH-Wert 4 oder weniger ist.
  11. Verfahren nach einem der vorstehenden Ansprüche, wobei
    die zweite Mischung einen pH-Wert-Zustand aufweist, der pH-Wert 6,8 oder weniger ist.
  12. Verfahren nach einem der vorstehenden Ansprüche, wobei
    das Metall mindestens eines ausgewählt aus der Gruppe ist, bestehend aus Bi, Hg, Cd, Pd, Zn, Tl, Ag, Pb und As.
  13. Verfahren nach einem der vorstehenden Ansprüche, wobei
    das Volumen der wässrigen Lösung des zweiten Chelatbildners weniger beträgt als das Volumen der Probe.
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